Wool dyestuffs of the anthraquinone series



Patented Mar. 26, 1940 WOOL DYEST'UFFS OF THE ANTI-IRA QUINONE SERIES Klaus Weinand, Leverkusen-I. G. Werk, and Kurt Bamberger, Gologne-Mulheim, I Germany, as-.

signers to General Aniline & Film Corporation, a: corporation of Delaware No Drawing. Application: July 22, 1938', Serial No. 220,698; In Germany July 26, 193': t H

4 Claims. (01. 260-371) Our present invention relates to new and valuable .wool dyestuffs and to a process of making the same, 1 I

Our new dyestuffs correspond to the general 5' formula O IITH:

wherein X stands for a member of the group consisting of the radicals v lil. z1 I? I z1 N-C5Ha I /Za N-CBHa .a

Son -as. f aud sol o c ns 2 0 Z1 standing for a member of the group consisting of hydrogen, halogen and an alkyl radical, Z2 standing'for a member ofzthe group consisting of hydrogen and an alkyl; radical, Z3 standing for a memberYof the group consisting of hydrogen,

halogen, an alkyl radical and a carbalkoxy radical,

Z4 standing for a member, of the group consisting of hydrogen and the SOsH-group, and R stands for a member of the group consisting of hydrogen,

. halogen, an alkyl radical or the SOQI-I-group.

It is to be understood that also those com- I pounds fall into the scope of our present inven-Y tion in which the carbon atoms1,9of the anthra quinone in the above formula form part of the pyridone or pyrimidonering and also those compounds in which the benzene nucleus of the anthraquinone indicated in the above formula with the letterD is substituted.

Our new dyestuiis are obtained by causing am 40 inoanthraquinones, pyridone anthrones or pyrimidone anthrones containing substituents which can be replaced by amino groupsto react with monoamino-benzene sulfonic acid-aryles-- ters or-monoamino-benzene sulfonic ac id-aryl-v amides and subjecting the compounds thus ob tained to a treatment'with sulfonation agents or by causing .l-amino-4-halogenanthraquinone-2- sulfonic acids to react'with monoamino-benzene sulfonic acid-arylesters or' monoamino-benz ene sulfonic acid-arylami-des respectively.

Assuitable sulfonation agents there may be mentioned concentrated sulfuric acid or chlorosulfonic acid.

The reaction is preferably carried out in thepresence of a copper salt, such as copper acetate or cuprous chloride, and in the presence of'an acid-binding agent. I are, for instance, the alkali and earth alkali metal salts of weak acids, such as sodium acetate, sodium carbonate or sodium bicarbonate. The presence of an indiiferent solvent may be advantageous. The corresponding aminoaryl' 'sulfonic acid derivative itself employed in an excess may also act as solvent.

The new dyestufis dye wool already from a Q neutral bath. In this re'sp ect. they are superior to the hitherto known wool dyestufis of the anthraquinone series. .The dyes are also distinguished by an excellent fastness to washing and fulling.

In order to further illustrate our invention the following examples are given, but we wishit however to be understood that our invention is not limited to the particular products or the reaction conditions stated therein.

The following examples illustrate the invention without, however, restricting it thereto, the

parts being by weight:

r v Example 1 I A mature of 52 parts of 1-amino-2-methyl-4- bromoanthraquinone, .250 parts of m-sulfanilic acid methylanilide (obtainable by condensing m- ,nitrobenzen'e-sulfochloride with methylaniline and reducing-thenitro group), 50 parts of anhydrous sodium acetate and Sparts of copper acetate are heated to 130-140" C. for 16 hours. The 7 reaction product obtained by Working up the melt in the usual manner with dilutehydrochloric acid is suitably purified by recrystallizing it from ani- Such acid-binding agents line; then the product is sulfonated by means'of fuming sulfuric acid containing 510% of S03. The dyestuif thus obtained which corresponds to the following formula U so,-'N I yields. on wool from a neutral or weakly acid bath bright violet shades.

By using m'-sulfanilic acid anilide or -ptoluidi'de instead of m-sulfanilic acid methylanilide, dyestuffs of similar properties are obtained.

When the 1eamino-Z-methyl--bromoanthraquinone is substituted by the equivalent quantity of 1-amino2-methy1-4-chloroanthraquinone, dyestuffs are obtained which are identical to those as described above.

Example 2 (H) NH2 and yielding on Wool from a neutral or Weakly acid bath bright reddish blue shades.

Example 3 A mixture consisting of 10 parts of l-amino- 2.4-dibromo-6-chloroanthraquinone, 10 parts ofanhydrous sodium acetate, 40 parts of l-amino- 4-chlorobenzene-3-sulfomethylanilide, 1 part of copper acetate and 0.1 part of copper powder is heated to C. for 3 hours. The melt is worked up in the usual manner by adding ethyl alcohol.

When sulfonated the product thus obtained in.

oleum of a low percentage a dyestuff is' obtained corresponding to the following formula 0 NE H SOr-IIT CH3 yielding on wool from a neutral or weakly acid bath bright blue shades.

By using 1-amino-4-methyl-3-sulfomethylanilide instead of l-amino-4-chlorobenzene-3- sulfomethylanilide a similar dyestuif is obtained.

Example 4 A mixture consisting of 12 parts of 1-amino- 2.4,-dibrorno-6-sulfdimethylamido anthraquinone, 12 parts of anhydrous sodium acetate. 60 parts of m-sulfanilic acid methylanilide, 0.6 part of copper acetate and 0.2 part of cuprous chloride is The melt is worked up in the usual heated to 140-150 C. for 4-5 hours and the melt obtained worked up in the usual manner by diluting it with hot ethyl alcohol. By dissolving the product thus obtained in sulfuric acid monohy drate and adding fuming sulfuric acid containing 20% of S03 a dyestufi is obtained corresponding to the following formula and. yielding on wool from a neutral or weakly acid bath bright greenish blue shades.

A similar dyestuff is obtained by using l-amino- 2.4-dibromo-6su1fmethylanilido anthraquinone instead of l-amino-2.4-dibromo-6-sulfdi1nethy1- amide anthraquinone.

Example 5 A mixture consisting of 25 parts of l-aminh- 2.4-dibromoanthraquinone, 25 parts of anhydrous sodium acetate, 40 parts, of p-sulfanilic acid methylanilide (obtainable from N-acetyl-p-sulfanilic acid chloride and methylaniline and saponifying the acetyl group) 40 parts of amyl alcoho1, 2.5 parts of copper acetate and 1 part of cuprous chloride is heated to 115120 C. for about 40 hours while stirring. The melt thus obtained is worked up in the usual manner by diluting it with hot ethyl alcohol. The reaction product can be purified by recrystallizing it from 5 parts of pyridine. When sulfonated it by means of fuming sulfuric acid having a low SO3- content a dyestuff is obtained being similar to that of Example 2 andcorresponding to the following formula o NH:

but yielding dyes of somewhat more blue shades.

Emample 6 A mixture consisting of 12 parts of 4-bromo-N- methylanthrap'yridone, 12 parts of anhydrous sodium acetate, 1.2 parts of copper acetate and 60 parts of m-sulfanilic acid methylanilide is heated to C. for 2 hours. The reaction product .is separated in form of red needles by diluting the melt cooled down to a temperature of 80 C. with hot ethyl alcohol. It can be recrystallized from a mixture of glacial acetic acid and chlorobenzene. When sulfonated in voleum of 10% at room temperature 9. dyestuff is obtained correspending to the following formula which dyes wool from a neutral orweakly acid bath clear red shades,

Example 7 h A mixture consisting of 12;parts of l-amino- 2-methyl-4-bromoanthraquinone, 48 parts of msulfanilic acid phenylester (obtainable by condensing m-nitrobenzenewsulfochloride with phe-.

1101 and reducing the nitro group), 12 parts of anhydrous sodium. acetate and 1 part of copper acetate is heated to 180 C. for 2 hours while stirring. The melt is cooled down to a temperature of 80 C. and diluted with parts of hot ethyl alcohol; whereby the reaction product obtained separates. It can be'purified by recrystallizing it from pyridine. When sulfonated it in 35. fuming sulfuric acid containing less than 5% of S03 while cooling, a dyestuff is obtained which corresponds to the following formula Cg o I rfi-som and yields on wool from a neutral or weakly acid 1 bath bright violet shades.

Dyestuffs of similar properties are obtained by using instead of m-sulfanilic acid phenylester the corresponding p-cresylester or p-chlorophenylester.

Example 8 f A mixture consisting of parts of melted 1-;

'amino-4-methylbenzene-3-sulfomethylanilide, 15

parts of 1 methylamino 4 bromoanthraquinone, 6 partsof anhydrous sodium acetate and 1.5 parts of copper acetateis heated to 132 C. for 5 hours. I The melt is worked up in the usual manner by diluting it with ethyl alcohol. The, reaction product is purified by recrystallizing it from organic solvents.

A mixture of 5 parts of the product thus obtained, 3.2 parts of ammonium chloride and 3.2 parts of urea is heated to 184 C. for 6 hours in 45 parts of phenol, whereby pyrimidone ring formation is effected. The phenol melt is worked up in the usual manner. The reaction product thus obtained'is purified by recrystallizing it from organic solvents.

By sulfonating the reaction product in weak l 3 oleum va dyestuff is" obtained which corresponds to the following formula and dyes wool froma neutral or weak acid bath bright violet shades.

. Example 9 10 parts of l-amino-4 bromoanthraquinone-2- sulfonic acid sodium, 10 parts of m-sulfanilic acid-methylanilidalO parts of sodium bicarbonate, and 1 part of cuprous chloride is heated to boiling in a mixture of 150 parts of water and 56 On cooling parts of. ethyl alcohol'f'or 8 hours. the dyestufi obtained separates; it is filtered with suction and purified by repeatedly dissolving itin waterand separating it with sodium chloride. -'I-he dyestuff; crystallizes in form of needles which are soluble in water with a blue color. It correspondsto the following formula and yields on wool from an acid or neutral bath with an addition of Glaubers salt reddish blue shades.

A dyestufi of similar'properties is obtained by 5 using m-sulfanilicja'cid; phenylester instead 0 m-sulfanilic acid methylanilida p sample 10 10 parts of 1-amino-4-bromoanthraquinone-2- sulfonic acid sodium, 15 parts of l-methylaniline- 3-sulfophenylester, 10 parts of sodium bicarbonate and lpart of cuprous bromideare heated to boiling in a mixture of 150 parts of water and 50 parts of alcohol with reflux, until the color of the solution has become brightlyblue. The

'dyestuff which separates on coolingis worked up and purified in the usual manner.

It corresponds to the following formula I and dyes wool from an acid "Dyestuffs of similar properties are obtained by using instead of the 4=-methylaniline-3-sulfo phenylester the corresponding 4-methylaniline-3- p-chlorophenylester or the l-methylaniline-3- sulfomethylanilide.

Example 11 y 10 parts of 1-aminoA-bromoanthraquinone-Z sulfonic acid sodium, 15 parts of l-methylaniline- 3-sulfonic acid-2-carbomethoxy-phenylester, 10 parts of sodium bicarbonate and 1 part of cuprous chloride are heated to boiling in a mixture of 150 parts of water and 50 parts of alcohol with reflux for several hours. The dyestufi obtained which separates on cooling isfiltered with suction and purified by dissolving it in water and It crystallizes in form of blue needles which disvsolve in water with a bluecolor and dyes wool from a weakly acid or neutral bath with an additionof Glaubers salt bright reddish blue shades.

' A similar dyestuff is obtained by using instead of 4-1'nethylaniline-3-sulfonic acid-carbometh- V oxyphenylester the corresponding carboethoxyphenylester. V

The same dyestuff may be made by reacting 1- amino 4 bromoanthraquinone-2-sulfonic acid upon 4-methy1ani1ine-3-sulfo-o'-carboxyphenylester and subsequently esterifying the carboxyl group, for instance with dimethylor diethylsulfate in an alkaline solution. v

Instead of the above carboxy-phenylester deriv atives also the corresponding carboxymethylanilide derivatives maybe employed.

We'claim:

1. W001 dyestuffs of the following general formula I 50,

v o X.

w herein X stands for a member of the group consisting of the radicals Z1 standing for a member of the group consisting of hydrogen, halogen, and an alkyl radical, Z2 standing for a member of the group consisting of hydrogen and an alkyl radical, Z3 standing for a member of the group consisting of hydrogen,

halogen, analkyl radical and a; carbalkoxy radical, Z4 standing for a member of the group consisting of hydrogen and the SOaI-I-group, and R stands for a member of the group consisting of hydrogen, halogen, an alkyl radical and the SOsI-Lgroup the substituents for Z4 and B. being chosen in such a Way that the compounds contain at least one sulfonic' acid'group.

2. The compound of thefollowing formula The compound of the following formula COOOH;

4. The compound of the following formula 0 IIIHI SOr-N COOCH:

KLAUS WEINAND. KURT BANIBERGER. 

